Method for removing ash-forming constituents and sediment from alkaline petroleum residuum



Patented Jan. 13, 1 948 METHOD FOR REMOVING ASH-FORMING CONSTITUENTS AND SEDIMENT ALKALINE PETROLEUM RESIDUUM Edward F. Wadley, Baytown, Tex'., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application June l, 1945,

Serial No. 597,588

i 3 Claims. (Cl. 19638) 1 The present invention is directed to a process for the treatment of alkaline residua of petroleum. In most modern refining operations, crude oil is distilled into its various fractions (light and heavy naphtha, gas oil, lube stocks, etc.) in a present invention is an alkali metal petroleum sulfonate. Generally, a mixture of oil soluble sulfonates and'water soluble sulfonates will be employed. The amount of water used may vary 5 from 50% to 150% by volume of the bottoms to pipe still which consists of atmospheric and vacbe treated. Sulfuric acid of a concentration uum distillation columns packed with bubble caps. rangin from about 3 N. to about N. is em- It has been found that the quality of the lube oil ployed. The amount of sulfuric acid to be emcuts which are taken on the vacuum still can be played is determined by the alkalinity of the improved when caustic is injected between the 10 bottoms to be treated, enough sulfuric acid being atmospheric and vacuum stills. However, this used to neutralizethe bottoms. The amount of type operation impairs the quality of the fuel oil demulsifying agent employed may range from n or residua produced at this unit in that it conabout .05 to .3% by weight of the water.

tains excessive ash and alkalinity and is h e It has been found that for the successful treatundesirable for good quality fuel production, ment of these alkaline bottoms the treating agent Many schemes have been attempted for cheaply must contain the three components specified and successfully reducing the ash and alkalinity bove. No one of these comp nent n be r of alkaline bottoms, but most of them hav not omitted. This will be apparent from the followbeen too successful. ing table in which are compared th especiflcations It is desired to produce a fue1 having th folof bottoms treated respectively with water and lowing tests: demulsifying agent, with water alone, with wate;

and sulfuric acid and with water, sulfuric aci Alkahmty Less than 01% by and demulsifying agent. In the preparation of Less than 0.1% by wt. d 400 t f t saw 2% max (VOL) s ata cu 1c centime ers o wa er con- Sediment 05 by wt taming 0.4 gram of petroleum sulfonate (produced by heavily acid treating a phenol extract of a It is the Purp e of this invention to provide lube oil) and enough 6 N. H2504 to neutralize 400 a p ess W r fuels e g the above ficc. of fuel oil bottoms of 0.34 alkalinity were cations can be produced from alkaline bottoms added t 400 of t b tt h i t 7 shwmg the testsI was heated to 150 F. and Well agitated. Steam Per cent by Welght was then injected until the temperature reached f 200 R, after which the mixture was allowed to settle. After an 18-hour settling period, the oil 6 ment layer was withdrawn and tested. The data are This quality bottoms is usually sent to low summarizedasfollows:

Table Tests on Washed Oils Pmeis Desmpfim Alkalinity Ash Sediment B. s. a w.

(Eli! cent (percent (percent (per cent y wt.) by wt.) by wt.) by vol.)

Bot-toms washed with water and petroleum sulfonate 0. 29 0. 30 0. 02 l. 8 Bottoms washed with water 0.10 0. 16 0.05 6.0 Bottoms washed with water and H1804 0. 04 0.33 0. 52 Emulsion Bottoms washed with water and H33 04 and petroleum sulfonate.-. 0.05 0. 05 0. 04 2.0

grade bunker fuel or burned in the refinery as fuel.

According to the present invention, alkaline bottoms of the aforesaid character are treated with a mixture of water, sulfuric acid and a demulsifying agent at an elevated temperature.

It will be observed from this table that the only treatment which produced an oil satisfying the specifications heretofore recited was the treatment according to the present invention. It may be observed that each of the other treatments produced an oil which failed to meet the specifi- Ihe demulsifying agent preferred for use in the cations in at least two respects.

The nature and objects of the present invention having been fully described and illustrated, what I wish to claim as new and useful is:

1. A method for treating alkaline petroleum residua obtained v by, distilling hydrocarbon oil in contact with alkali which comprises. mixing said residua with from about 50% to 150% by volume of water, adding only sufiicient sulfuric acid of a strength ranging from about 3 N, to

about 10 N. to neutralize said; residua adding a petroleum sulfonate in an amountranging f rom about .05 to 3% by weight of the water, thoroughly mixing said materials atiangelevatedrtema perature, allowing the mixture to, settle: and'- stratify and withdrawing the oil layer.

2. A method according to Claim-1 il'h wllich thq petroleum sulfonate is an alkali metal petroleum;

volumes of water per volume of residuum, adding sulfuric acid of a strength ranging from about 3 N. to about 10 N. in an amount only sufiicient to neutralize the alkalinity of said residuum, adding petroleum sulfonate in amount; ranging from abqui o. y Wei ttof the w me timately mixing said residuum, water, acid and sulfonate at a temperature between about 125 and 212 F allowing the mixture to settle and stratify and withdrawing the oil layer.

The following references are of record in the 1 .6 qiilsisnateM:

UNITED STATES PATENTS Number Name Date 20 2,157,315 Archibald May 9, 1939 1;802,336 Cook Apr. 28', 1931 1,686,491 Hughes. et-al. Oct. 2, 1928 1-;785,242 Becker Dec. 16, 1930 

